EP0034240A2 - Procédé pour la préparation d'amides d'alpha-céto-acide carboxylique N-tertiaire-butylique - Google Patents

Procédé pour la préparation d'amides d'alpha-céto-acide carboxylique N-tertiaire-butylique Download PDF

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Publication number
EP0034240A2
EP0034240A2 EP81100034A EP81100034A EP0034240A2 EP 0034240 A2 EP0034240 A2 EP 0034240A2 EP 81100034 A EP81100034 A EP 81100034A EP 81100034 A EP81100034 A EP 81100034A EP 0034240 A2 EP0034240 A2 EP 0034240A2
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EP
European Patent Office
Prior art keywords
acid
tert
cyanide
methyl ether
iii
Prior art date
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Granted
Application number
EP81100034A
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German (de)
English (en)
Other versions
EP0034240B1 (fr
EP0034240A3 (en
Inventor
Gerhard Dr. Bonse
Heinz Ulrich Dr. Blank
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
    • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D253/075—Two hetero atoms, in positions 3 and 5

Definitions

  • the present invention relates to a new process for the preparation of ⁇ -ketocarboxylic acid N-tert-butylamides which can be used as intermediates for the synthesis of known herbicidal active compounds.
  • ketocarboxamides are valuable intermediates for the preparation of herbicidally active 1,2,4-triazin-5-one derivatives which, e.g. according to DE-OS 21 65 554 from ⁇ -ketocarboxamides and hydrazine derivatives are easily accessible.
  • acyl cyanides are also accessible to the Ritter reaction in the same way.
  • Acta Chem. Scand. 22, pp. 1787-1790 (1968) the preparation of phenylglyoxylic acid N-tert. butylamide from benzoyl cyanide and tert-butanol in the presence of Lewis acids in a yield of 72% of theory.
  • DE-OS 27 33 180 and DE-OS 27 33 181 it is also possible to produce phenylglyoxylic acid N-tert-butylamide and other glyoxylic acid - N-tert-butylamides by reacting the corresponding acyl cyanides with tert-butanol or isobutylene as components which form tert-butyl carbonium ions in the presence of strong acids (for example concentrated sulfuric acid), ie under the conditions of the Ritter reaction, in yields of 54-95% of theory.
  • strong acids for example concentrated sulfuric acid
  • R represents an optionally substituted aliphatic radical with up to 8 carbon atoms, for an optionally substituted cycloalkyl radical with 3 to 6 carbon atoms, for an optionally substituted phenyl or naphthyl radical or for an optionally substituted heterocyclic radical, obtained in high yields and in high purity if acyl cyanides of the general formula II where R has the meaning given above, with tert-butyl methyl ether of the formula III at temperatures between 0 and 80 ° C in the presence of an acid which is capable of activating the ether (III) under the reaction conditions to a t-butyl carbonium ion, and optionally in the presence of a solvent and then hydrolyzing the reaction mixture in a manner known per se .
  • the implementation of the invention is carried out under the conditions of the aforementioned "Ritter reaction". It is particularly surprising that - in each case in particular in the case of approximately stoichiometric batches - using the reaction according to the invention to achieve significantly higher yields than when using t-butanol or isobutylene as the source of t-butyl carbonium.
  • R preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, it being possible for any of these alkyl radicals to be substituted by alkoxy with 1 to 4 carbon atoms, carbalkoxy with 1 to 4 carbon atoms in the alkoxy group, nitro, nitrile and / or halogen, such as fluorine, chlorine, bromine or iodine; furthermore R preferably represents optionally by alkyl, alkoxy or carbalkoxy each having up to 4 carbon atoms, nitro, nitrile and / or halogen, such as fluorine, chlorine and Bromine, substituted cycloalkyl with 5 or 6 carbon atoms in the ring system.
  • R preferably represents phenyl or naphthyl optionally substituted by alkyl, alkoxy or carbalkoxy each having up to 4 carbon atoms, nitro and / or halogen, such as fluorine, chlorine and bromine;
  • R preferably represents 5- or 6-membered heterocyclic radicals which contain 1 to 3 heteroatoms and are optionally substituted by alkyl, alkoxy or carbalkoxy each having up to 4 carbon atoms, nitro, nitrile and / or halogen, such as fluorine, chlorine and bromine such as may contain oxygen, sulfur and / or nitrogen in the ring and may also be fused with a benzene ring.
  • heterocyclic radicals which are particularly suitable are: morpholinyl, imidazolyl, pyrazolyl, pyrrolyl, isoxazolyl, piperidinyl, oxazolyl, 1,2,4-triazol-1-y1, 1,2,4-triazol-4-yl, 1,2,3-triazolyl, 1,2,4-thiadiazol-2-yl, benzimidazolyl and furanyl.
  • acyl cyanides of the formula (II) are known; Acyl cyanides not yet known can be prepared by known processes (cf. Angew. Chem. 68, pp. 425-435 (1965); furthermore DE-OSs 26 14 240, 26 14 241, 26 14 242, 27 08 182, 27 08 183).
  • Acyl cyanides include pivaloyl cyanide and benzoyl cyanide.
  • Tert.-butyl methyl ether (III) is available on an industrial scale and is commercially available.
  • the reaction according to the invention is carried out in the presence of an acid which is able to activate the ether (III) under the reaction conditions to give a t-butyl carbonium ion.
  • the reaction temperature can be varied within a wide range. In general, as indicated above, temperatures between 0 and 80 ° C, preferably between 10 and 40 ° C.
  • the subsequent hydrolysis is advantageously carried out using ice water.
  • the reaction is generally carried out at normal pressure.
  • the reaction can be carried out in the absence or in the presence of a solvent or solubilizer.
  • a solvent or solubilizer Certain organic solvents can be used as solubilizers; glacial acetic acid and dichloromethane, dialkyl ethers such as diethyl or diisopropyl ether and diaryl ethers such as e.g. Diphenyl ether.
  • dialkyl ethers such as diethyl or diisopropyl ether
  • diaryl ethers such as e.g. Diphenyl ether.
  • the acids required for carrying out the process according to the invention are used in a stoichiometric or superstoichiometric amount.
  • 1 to 5 mol, preferably 1.1 to 1.5 mol, of acid are used per 1 mol of acyl cyanide of the formula (II).
  • the acid or a mixture of solvent and acid is initially taken and a mixture of the two other components, acyl cyanide and t-butyl methyl ether, optionally in solvent, is added.
  • the reaction times are generally 1-10 hours.
  • the reaction mixture is then most conveniently poured onto ice.
  • the ⁇ -ketocarboxamides formed can be isolated by filtration or by extraction.
  • Suitable extractants for this purpose are water-immiscible solvents, for example ethers such as diethyl ether or diisopropyl ether, esters such as ethyl acetate, ketones such as methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane, chlorobenzene or dichlorobenzene, and also aromatics such as benzene, toluene, and ethylbenzene , Cumene or nitrobenzene.
  • Dichloromethane is preferably used. It is also possible to use excess tert-butyl methyl ether (III) which has been used as a solvent and has not entered the reaction at the same time as an extractant in the workup; this can be reused after distillation.
  • d-ketocarboxamides of the formula (I) which can be prepared according to the invention are known; for example, they can be used as intermediates for the synthesis of herbicidal active compounds.
  • trimethylpyruvic acid N-tert-butylamide (Ia) gives the herbicidally particularly active compound 4- A mino-6-tert-butyl-3-methylthio-1,2,4-triazine-5 according to the following reaction scheme (4H) -one (VI) (cf. DE-PS 17 95 784):
  • reaction mixture After stirring for 4 hours, the reaction mixture is poured onto 100 g of ice and stirred for a further 30 minutes. The mixture is then diluted with 75 ml of methylene chloride, the organic phase is separated off and the methylene chloride solution is evaporated.
  • This example illustrates a preferred mode of operation in accordance with the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP81100034A 1980-01-22 1981-01-07 Procédé pour la préparation d'amides d'alpha-céto-acide carboxylique N-tertiaire-butylique Expired EP0034240B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3002203 1980-01-22
DE19803002203 DE3002203A1 (de) 1980-01-22 1980-01-22 Verfahren zur herstellung von (alpha)-ketocarbonsaeure-n-tert.-butylamiden

Publications (3)

Publication Number Publication Date
EP0034240A2 true EP0034240A2 (fr) 1981-08-26
EP0034240A3 EP0034240A3 (en) 1981-09-16
EP0034240B1 EP0034240B1 (fr) 1983-04-13

Family

ID=6092678

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81100034A Expired EP0034240B1 (fr) 1980-01-22 1981-01-07 Procédé pour la préparation d'amides d'alpha-céto-acide carboxylique N-tertiaire-butylique

Country Status (7)

Country Link
US (1) US4345100A (fr)
EP (1) EP0034240B1 (fr)
JP (1) JPS56104853A (fr)
BR (1) BR8100321A (fr)
DE (2) DE3002203A1 (fr)
DK (1) DK159417C (fr)
IL (1) IL61928A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0712835A2 (fr) 1990-12-31 1996-05-22 Basf Aktiengesellschaft Procédé de préparation d'esters d'acides cétocarboniques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1051462B (de) * 1955-10-26 1959-02-26 Hermann Schneider Kleinbehaelter zur Abgabe und Aufnahme von Fluessigkeiten, vorzugsweise Parfuems und aehnlichen Kosmetika
EP0549531A1 (fr) * 1991-12-20 1993-06-30 Säurefabrik Schweizerhall Procédé de préparation d'anhydrides d'acides
CN109096139B (zh) * 2018-09-03 2021-03-02 贵州大学 一种α-羰基酰胺衍生物的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2518156A (en) * 1949-01-25 1950-08-08 Du Pont Reaction of ethers with nitriles
DE2733180A1 (de) * 1977-07-22 1979-01-25 Degussa Verfahren zur herstellung von 1,2,-triazin-5-on-derivaten
DE2733181A1 (de) * 1977-07-22 1979-02-08 Degussa Verfahren zur herstellung von n-substituierten alpha-ketocarbonsaeureamiden

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2236040C2 (de) * 1972-07-22 1974-06-27 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Carbonsäureamiden

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2518156A (en) * 1949-01-25 1950-08-08 Du Pont Reaction of ethers with nitriles
DE2733180A1 (de) * 1977-07-22 1979-01-25 Degussa Verfahren zur herstellung von 1,2,-triazin-5-on-derivaten
DE2733181A1 (de) * 1977-07-22 1979-02-08 Degussa Verfahren zur herstellung von n-substituierten alpha-ketocarbonsaeureamiden

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0712835A2 (fr) 1990-12-31 1996-05-22 Basf Aktiengesellschaft Procédé de préparation d'esters d'acides cétocarboniques

Also Published As

Publication number Publication date
IL61928A0 (en) 1981-02-27
IL61928A (en) 1984-03-30
DK159417B (da) 1990-10-15
EP0034240B1 (fr) 1983-04-13
BR8100321A (pt) 1981-08-11
JPH0141617B2 (fr) 1989-09-06
DE3002203A1 (de) 1981-07-23
DK26881A (da) 1981-07-23
JPS56104853A (en) 1981-08-20
US4345100A (en) 1982-08-17
EP0034240A3 (en) 1981-09-16
DE3160155D1 (en) 1983-05-19
DK159417C (da) 1991-03-04

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